Review
Chemistry, Multidisciplinary
Zaozao Qiu, Zuowei Xie
Summary: Carborynes, three-dimensional analogues of benzyne, can be generated in situ from specific precursors. They are useful for synthesizing various functionalized carborane derivatives and exhibit unique properties. Carborynes exhibit pericyclic reaction modes similar to benzyne, but also have their own distinctive features. Previous research has explored the unique reaction modes and mechanisms of carborynes.
CHEMICAL SOCIETY REVIEWS
(2022)
Article
Chemistry, Multidisciplinary
Jie Zhang, Zuowei Xie
Summary: o-Carboryne is a useful synthon for the synthesis of carborane-functionalized molecules, undergoing efficient cycloaddition reactions with various conjugated enynes. The reaction generates carborane-fused tricyclic compounds in moderate to high yields, providing a convenient strategy for the construction of complex carborane-functionalized molecules.
Article
Chemistry, Organic
Yifan Zhang, Yuxin Jiang, Yi Wang, Tianyi Sun, Yuanjie Meng, Yueyan Huang, Xiaoqing Lv, Jinlai Gao, Xiaoqin Zhang, Shilei Zhang, Shihui Liu
Summary: In this study, a distinctive photoredox/copper dual-catalyzed esterification of benzylic C-H bonds was reported, which involves the combination of photoredox-mediated hydrogen atom transfer and Cu(II)-mediated radical-polar crossover. The methodology shows a high functional group tolerance (>40 examples) and moderate to good yields with structurally diverse benzylic C-H substrates. Notably, stoichiometric amounts of carboxylic acids are used as coupling partners, enabling the synthesis of structurally diverse benzylic esters and the late-stage functionalization of pharmaceuticals.
Article
Chemistry, Applied
Jun Liang, Yingying Wang, Xiangcheng Li, Ming Xu, Shaochun Shen, Chuang Liu, Wenhua Fu, Weichuan Tao, Zhiqing Yuan, Zhendong Wang, Weimin Yang
Summary: XBMPOH is a novel quaternary ammonium hydroxide used as an organic structure-directing agent for the synthesis of BEC zeolites. It shows better crystallization capabilities, especially in the Al containing system, compared to commonly used OSDA.
MICROPOROUS AND MESOPOROUS MATERIALS
(2021)
Article
Chemistry, Inorganic & Nuclear
Liping Guo, Shaowu Wang, Zuowei Xie
Summary: Rare-earth metal carboryne complexes were synthesized using either an alkane elimination reaction or a salt metathesis reaction. Single-crystal X-ray analyses confirmed the molecular structures, showing a unique three-membered ring between the rare-earth metal and two cage C atoms. These complexes underwent ring-expansion reactions with various unsaturated organic compounds to form five-membered metallacycles.
Article
Chemistry, Organic
Jie Zhang, Zuowei Xie
Summary: At room temperature, o-carboryne efficiently undergoes ene reaction with a variety of alkynes and alkenes possessing an aCH proton, yielding a series of o-carboranyl allenes and alkenes in good yields. This reaction has a broad substrate scope and provides a facile synthetic method for obtaining cage C-substituted carboranyl allenes and alkenes, which can be utilized as useful starting materials for synthesizing multifunctionalized carboranes.
Article
Chemistry, Organic
Pengcheng Huang, Xipeng Jiang, Du Gao, Cheng Wang, Da-Qing Shi, Yingsheng Zhao
Summary: A highly regioselective Friedel-Crafts alkylation of arenes was developed using hexafluoroisopropanol as a promoter. Various arenes, including anilides, anisoles, and phenols, were compatible with the reaction, yielding para-alkylated products in moderate to excellent yields. Mechanistic studies showed that hexafluoroisopropanol acted as a weak Lewis acid to activate haloalkanes and coordinated with arenes through hydrogen bonding, leading to highly para-selective alkylated products.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Thermodynamics
Carson Chu, Mohammed H. Zaher, Murray J. Thomson
Summary: This study assessed the temperature sensitivity of n-propylbenzene and 1,2,4-trimethylbenzene on soot formation in coflow diffusion flames. The results showed that increasing the temperature led to higher soot volume fractions and primary particle diameters, but alkyl benzenes exhibited lower temperature sensitivity. The model indicated that raising the reactant temperature did not significantly affect the production of soot precursor PAH, but altered the available time for soot growth, promoting soot formation. Furthermore, the impact of fuel temperature on soot formation was more pronounced along the centerline.
COMBUSTION AND FLAME
(2022)
Article
Thermodynamics
Daniel J. Carlson, Neil F. Giles, W. Vincent Wilding, Thomas A. Knotts
Summary: The TLVMie force field has been extended to include compounds with alkyl branching, and its accuracy in predicting liquid viscosity and density has been evaluated. It outperforms other methods in viscosity prediction accuracy and transferability to compounds with limited experimental data.
FLUID PHASE EQUILIBRIA
(2023)
Article
Chemistry, Physical
Deependra Parmar, Seung Hyeok Cha, Chenfeng Huang, Hsu Chiang, Seth Washburn, Lars C. Grabow, Jeffrey D. Rimer
Summary: This study developed structure-performance relationships by considering a broad class of zeolite framework structures. Seven different medium-pore zeolites were synthesized and tested in a toluene alkylation with methanol reaction. Zeolite MCM-22 exhibited high selectivity and long lifetime. The study also revealed the effect of high pressure and coke formation on the performance of MCM-22.
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Analytical
Ashur S. Rael, Courtney A. Cruse, Magnus Rydberg, John Goodpaster
Summary: Recent advancements in benchtop VUV spectrometers have led to effective universal detectors in gas chromatography (GC), offering an alternative to the gold standard of mass spectrometry (MS). The potential applications of GC/VUV, particularly in the analysis of ignitable liquids like alkylbenzenes found on debris from suspected arson fires, have been highlighted. Comparisons between GC-VUV and GC-MS for alkylbenzene analysis showed superior specificity and sensitivity in the former, with LODs in picograms on column.
Article
Chemistry, Organic
Xia Lin, Chengtao Fang, Xiaolei Huang, Xiaohui Xiao
Summary: A novel method for synthesizing 1,1,2-tribromoethyl arenes was developed in this work, with the additional discovery that under strong acidic conditions, a selectivity switch can lead to the formation of alpha-bromoketones.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Environmental Sciences
Roxanny Helen De Arruda-Santos, Bruno Varella Motta da Costa, Paulo Sergio Martins de Carvalho, Eliete Zanardi-Lamardo
Summary: The Capibaribe Estuarine System (CES) located in the Brazilian Northeast is a tropical estuary that provides multiple ecosystem services but is facing visible environmental degradation due to domestic and industrial effluents. This study evaluated the contamination level of domestic sewage and the contribution of organic carbon sources in sediments. The results indicate that sewage inflow triggers eutrophication of CES, and the system is moderately contaminated by linear alkylbenzene (LAB), suggesting retention of sewage. Improved policies are urgently needed to reduce contamination of estuarine environments and protect public health.
ENVIRONMENTAL POLLUTION
(2023)
Article
Environmental Sciences
Cristiane Cassiolato Pires Hardoim, Andressa Cristina Ramaglia, Josilene da Silva, Satie Taniguchi, Rafael Andre Lourenco
Summary: The study assessed polycyclic aromatic hydrocarbons and linear alkylbenzenes in sediments from shallow areas of the Sa tilde o Sebastia tilde o channel in southeastern Brazil. Despite relatively low concentrations compared to deeper areas, the contamination reflected the sediment pattern of the channel.
MARINE POLLUTION BULLETIN
(2021)
Article
Chemistry, Multidisciplinary
Jordi Poater, Clara Vinas, Silvia Escayola, Miquel Sola, Francesc Teixidor
Summary: This study provides experimental and computational evidence that the C-C bond formed between two adjacent carbons that lose H atoms in o-carboryne is different from that in o-benzyne. While the C-C bond in o-benzyne behaves as a triple bond, the C-C bond in o-carboryne is a double bond. Therefore, 1,2-dehydro-o-carboryne should be called o-carborene instead of o-carboryne.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Biao Cheng, Yu Chen, Peng Zhou, Zuowei Xie
Summary: A new method for the trifunctionalization of o-carboranes has been developed, leading to the synthesis of a new class of B(3,4,5)-trisubstituted o-carborane derivatives. This method involves a series of reactions and represents a new strategy for the catalytic selective polyfunctionalization of carboranes with different substituents, achieving high yields of the desired products.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Organic
Lin-Bao Zhang, Zuowei Xie
Summary: A highly efficient Ir-catalyzed regioselective cage B(4)-H acylmethylation of o-carboranyl acids using sulfoxonium ylides as alkylating regents has been developed, leading to the preparation of a large class of B(4)-acylmethylated o-carboranes in good to excellent yields with a broad substrate scope under redox neutral conditions.
Article
Chemistry, Multidisciplinary
Xiaofeng Mao, Jie Zhang, Zhenpin Lu, Zuowei Xie
Summary: A tetra(o-tolyl)(mu-hydrido)diborane(4) anion 1 was synthesized and found to form eta(2)-B-B bonded complexes 2 with NHC-coordinated transition-metal halides, where the elongation of B-B bonds is most significant in the gold complex.
Article
Materials Science, Multidisciplinary
Ming Chu, Jie Zhang, Xingwei Zeng, Zefeng Chen, Danqing Liu, Han Chen, Zuowei Xie, Jianbin Xu, Qian Miao
Summary: Molecules of 12-o-carboranyldodecylphosphonic acid can form a novel self-assembled monolayer on alumina, effectively tuning charge carriers in organic field effect transistors by assembling dipoles at the semiconductor-dielectric interface. This SAM enables p-channel OFETs of pentacene and ambipolar charge transport in n-type organic semiconductors like chlorinated tetraazapentacene, while the surface electrostatic potential of the SAM correlates with the observed shift of threshold voltage in OFETs.
JOURNAL OF MATERIALS CHEMISTRY C
(2022)
Article
Chemistry, Multidisciplinary
Jie Zhang, Zuowei Xie
Summary: This study reported a pyridine-enabled transition-metal-free regioselective nucleophilic aromatic cage B(4)-H amination reaction, offering a selective amination strategy for o- and m-carboranes. Control experiments indicated the crucial role of magnesium complex, bidentate ligand, and reaction temperature in the process of cage isomerization.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Huifang Zhang, Ruofei Cheng, Zaozao Qiu, Zuowei Xie
Summary: An efficient Ir-catalyzed cage boron alkenylation of 1-(2 '-picolyl)-o-carboranes with diarylacetylenes has been developed, leading to a wide variety of B-H geminal addition products via 1,2-carbon migration of alkynes. The steric effect of cage carbon substituents has a great impact on the regioselectivity of such alkenylation reactions.
CHEMICAL COMMUNICATIONS
(2023)
Editorial Material
Chemistry, Organic
Varinder K. K. Aggarwal, Zuowei Xie, Hajime Ito
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Liping Guo, Shaowu Wang, Zuowei Xie
Summary: Rare-earth metal carboryne complexes were synthesized using either an alkane elimination reaction or a salt metathesis reaction. Single-crystal X-ray analyses confirmed the molecular structures, showing a unique three-membered ring between the rare-earth metal and two cage C atoms. These complexes underwent ring-expansion reactions with various unsaturated organic compounds to form five-membered metallacycles.
Article
Chemistry, Multidisciplinary
Yik Ki Au, Qiangqiang Ma, Jie Zhang, Zuowei Xie
Summary: An efficient and convenient strategy for Ir-catalyzed selective B(3)-amination of o-carboranes with amines via acceptorless BH/NH dehydrocoupling was developed, resulting in a series of B(3)-aminated-o-carboranes with moderate to high yields and H2 gas as the sole by-product. The oxidant-free system demonstrates sustainability, atom-economy, and environmental friendliness. A reaction mechanism involving an Ir(I)-Ir(III)-Ir(I) catalytic cycle with oxidative addition, dehydrogenation, and reductive elimination was proposed.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Zhen Nie, Ruofei Cheng, Zaozao Qiu, Zuowei Xie
Summary: 4-Bpin-o-carborane exhibits a unique reactivity with ketones under basic conditions, leading to sequential cage carbon alkylation, B-B bond activation, and unexpected O-migration. The reaction is compatible with a wide range of substrates including dialkyl or alkyl aryl ketones. The proposed reaction mechanism involves cage CH deprotonation, nucleophilic attack of ketone, and O-migration along with B-B bond cleavage.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Shimeng Li, Yizhen Liu, Zuowei Xie
Summary: This work presents a general method for synthesizing sulfenylated and selenylated carboranes at room temperature using iodocarboranes as starting materials. The generation of hypervalent boron radicals via a visible light-promoted Pd(0)/Pd(I) pathway allows for the convenient construction of B-S/Se bonds.
CHINESE JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Physical
Huifang Zhang, Jie Zhang, Zaozao Qiu, Zuowei Xie
Summary: The intrinsic chirality of three-dimensional carborane derivatives was established by studying the substitution patterns. Through the addition of functional groups, the symmetrical o-carborane can be transformed into chiral-at-cage structures. An Ir-catalyst-promoted asymmetrical (S)-B(4)-H activation method under mild reaction conditions was developed, achieving high efficiency with up to 99% enantioselectivity.
Article
Chemistry, Organic
Jie Zhang, Zuowei Xie
Summary: This paper summarizes the recent developments in base metal-catalyzed regioselective B-H functionalization of carboranes, particularly in the regio- and enantio-selective cage B-H derivatization among ten chemically similar BH vertices in o-carboranes. While precious transition metal-catalyzed cage B-H functionalization has made significant advances in diversely functionalized o-carboranes, research on B-H functionalization via a base metal catalysis strategy has just begun recently.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Multidisciplinary
Hairong Lyu, Zuowei Xie
Summary: A unique approach to vertex-selective catalytic B-H amination has been developed, allowing the reaction to occur at either the B(3)- or B(4)-position in o-carboranes. By using different transition metal catalysts, the dehydrogenative BH/NH cross-coupling of o-carboranes and free amines has been achieved, resulting in a wide variety of B(3)- or B(4)-aminated o-carboranes with high regioselectivity.
CHEMICAL COMMUNICATIONS
(2022)
Review
Chemistry, Multidisciplinary
Zaozao Qiu, Zuowei Xie
Summary: Carborynes, three-dimensional analogues of benzyne, can be generated in situ from specific precursors. They are useful for synthesizing various functionalized carborane derivatives and exhibit unique properties. Carborynes exhibit pericyclic reaction modes similar to benzyne, but also have their own distinctive features. Previous research has explored the unique reaction modes and mechanisms of carborynes.
CHEMICAL SOCIETY REVIEWS
(2022)
